TW201536409A - Jet loop reactor with nanofiltration and gas separator - Google Patents

Abstract

The invention relates to a device for the continuous homogeneous catalytic reaction of a liquid with a gas and optionally a further fluid, wherein the device comprises at least one jet loop reactor having an external liquid circuit driven by at least one pump, and wherein the device has at least one membrane separation unit, preferably retaining the homogeneous catalyst, which membrane separation unit is arranged in the external liquid circuit of the jet loop reactor. The object thereof is to reduce the costs of the device. This is achieved by providing an additional apparatus, namely a gas separator, which is arranged in the external liquid circuit of the jet loop reactor and is installed for separating off gas from the external liquid circuit and feeding it back into the jet loop reactor.

Description

Jet loop reactor and gas separator with nanofiltration

The invention relates to a device for the continuous homogeneous catalytic reaction of a liquid with a gas and optionally another fluid, wherein the device comprises at least one jet loop reactor having an external liquid loop driven by at least one pump, and wherein The apparatus has at least one membrane separation unit, preferably retaining the homogeneous catalyst, the membrane separation unit being disposed in an outer liquid loop of the jet loop reactor.

A free-flowing medium in which the liquid system is substantially incapable of being compressed. A free flowing medium that can be compressed by a gas system. Flow system liquid or gas. In the case of the present invention, the homogeneous mixture of the liquid phase and the two phase mixture of the gas phase which are distributed in a distributed manner is likewise a fluid. Because of the percentage of gas, these flow systems can be compressed to a small extent.

In the context of the present invention, a feed liquid is taken to mean a substance or a mixture of substances which, under the reaction conditions, is present in the liquid state of the object. In the apparatus, and having at least one reactant. Gas is taken to mean a pure gas or gas mixture having at least one reactant and optionally an inert gas. An example of a gas having a direactant is a synthesis gas composed of hydrogen and carbon monoxide, which is used, for example, in hydroformylation.

In the case of the present invention, a jet loop reactor is a device for the continuous reaction of a liquid and at least one other fluid, wherein the liquid passes under pressure through a nozzle into the reaction space and flows therethrough in a main flow direction. Reversing at the end of the reaction space opposite the nozzle, backflowing against the main flow direction, and being accelerated again in the main flow direction, thereby causing an internal liquid loop (loop) to be established in the reaction The way inside the space. The second fluid is entrained by the flow of the liquid and reacts along the circuit along the path. This liquid is thus used as a driving jet medium. To input the kinetic energy into the liquid, an external liquid loop is assigned to the reaction space, and a portion of the liquid's external liquid loop circulates outside the reaction space in the loop. Within the outer liquid loop, a pump is provided that imparts the desired kinetic energy to the liquid stream for establishing the loop flow within the reactor. The nozzle is accordingly fed by the outer loop.

A good introduction to the technology of the jet loop reactor is provided in: P. Zener, M. Claus: "Blister Tower", Ullmann Industrial Chemistry Encyclopedia, Electronic Publications, 7th Edition, Chapter 4, Wiley-VCH, Wilhelm [2005].

In the hydroformylation (also referred to as carbonylation reaction), a hydrocarbon having an olefinic double bond (olefin) is reacted with a synthesis gas (a gas mixture of hydrogen and carbon monoxide) to form acetaldehyde and/or ethanol.

The introduction of the principle of hydroformylation is provided in: Falbe, Jürgen: a new composition with carbon monoxide. Springer 1980, Berlin, Heidelberg, New York und Plut, Roy L: hydroformylation. Development in Organometallic Chemistry, Vol. 17, pp. 1-60, 1979.

A good overview of the state of hydroformylation of olefins can be found in B. Kornis, WA Hermann, "Homogeneous Catalysis with Organic Metal Compounds", Volumes 1 & 2, VCH, Weemheim, New York, 1996 Also in R. Franca, D. Selent, A. Berna, "Application Hydroformylation", Chemical Issues, 2012, DOl: 10.1021/cr 3001803.

Hydroformylation has the effect of producing higher acetaldehyde. In particular, higher acetaldehyde oximes having from 3 to 25 carbon atoms are used as precursors for the synthesis, for the production of carboxylic acids, and as odorants. Industrially, they are often converted to the corresponding ethanol by catalytic hydrogenation, which in turn has the effect of producing plasticizers and detergents. Because of the large-scale industrial importance of this hydroformylation product, the carbonylation reaction is carried out on an industrial scale.

In this large-scale industrial hydroformylation, a cobalt or ruthenium-based organophosphorus metal composite catalyst is currently used. The catalysts are homogeneously dissolved in the liquid hydroformylation mixture. In the case where the target product (the aldehyde) is separated from the hydroformylation mixture, since the composite catalyst reacts more sensitively to change in the state and lose its activity, the homogeneous catalyst must also be It is separated from the hydroformylation mixture under mild conditions.

Conventionally, the catalyst is separated from the hydroformylation mixture by distillation. In order to reduce the risk of deactivation and reduce the energy consumption of the process, Efforts have been made to separate the homogeneously dissolved catalyst from the hydroformylation mixture using a membrane technique (nanofiltration). The excellent introduction into the diaphragm technology is given by: Melin/Rautenbach: Membranverfahren. Grundlagen der Modul-und Anlagenauslegung. [Separator process. Principles of module and system design] Springer, Heidelberg, Berlin 2004.

The principle of membrane-supported, organophilic nanofiltration for separation of homogeneously dissolved catalyst composites and hydroformylation mixtures is described by Priske, M. et al.: Homogeneous catalysts for the hydroformylation of higher olefins The separation is integrated by the reaction of the organophilic nanofiltration. Journal of Diaphragm Science, Vol. 360, No. 1-2, September 15, 2010, pages 77-83; doi: 10.1016/j.memsci.2010.05.002.

In the membrane filtration of the hydroformylation reactor effluent, a synthesis gas system which is often dissolved or not dissolved in the liquid reactor effluent is characterized in that the hydroformylation is a two-phase reaction in which hydrogen and carbon monoxide form the gas. The olefin, acetaldehyde and ethanol form the liquid phase, wherein the catalyst is dissolved without solid phase. A portion of the synthesis gas is also dissolved in the phase of the liquid reactor in accordance with the equilibrium of the solution in the reactor and is removed with the reactor effluent. Although the synthesis gas remains dissolved in the reactor effluent during filtration of the membrane, the membrane filtration is not problematic to this extent. However, if the liquid reactor effluent is accompanied by a gas phase, or if the gas phase forms a bubble when the membrane is relaxed, the gas bubble can mechanically damage the membrane. Polymeric membranes are especially susceptible to damage by air bubbles.

Another problem is the loss of carbon oxides due to degassing synthesis gas: especially It is the rhodium-catalyzed hydroformylation which exerts a critical effect on the activity and stability of the catalyst composite. In order to avoid loss of activity during the separation of the homogeneously dissolved composite catalyst from the reaction effluent membrane of the hydroformylation, EP 1 193 472 B1 proposes all three connections (feedstock, retentate, permeate) in the membrane separation unit. Ensure a minimum CO partial pressure.

WO2010023018A1 shows a two parallel connected jet loop reactor with a shared external liquid loop. The jet loop reactor is used in the hydroformylation with a homogeneous dissolved catalyst. Separation of the catalyst is not the subject of discussion.

Jensen, M., Wilting, J., Muller, C. and Vogt, D. (2010), 1-octene with polyhedral alkane oligo (POSS) amplifying triphenylphosphine Continuous ruthenium catalyzed hydroformylation, Applied Chemistry International Edition, 49:7738-7741, doi:10.1002/anie.201001926 describes the implementation of homogeneous catalytic hydroformylation in a special spray reactor containing each other in a cross flow chamber Two external liquid loops in contact. In the first cycle, the liquid reactor effluent is removed from the reactor by the synthesis gas dissolved therein and circulated by the impeller pump. In the cross flow chamber, the reactor effluent is split into two substreams: a first substream containing liquid reactor effluent having dissolved synthesis gas is conducted as a synthesis gas in the gas phase along the first cycle Into the reactor. The substream of the second pure liquid is transported through the ceramic membrane separation unit by means of a pump. Here, the target product is taken as a permeate, and the catalyst-containing retentate is passed back through the second circulation line to the cross flow chamber where it is mixed with the first liquid. The advantage of this device is considered that the reactor effluent is degassed within the cross flow chamber and thus any gas phase produced remains in the first cycle. This is because the particular flow conditions of the cross flow chamber facilitate the removal of the bubble into the backflow of the first loop. The second liquid loop configuration of the membrane thus remains free gas (H ₂ and CO which means remains dissolved in the liquid). However, the disadvantages of this laboratory device are its more complicated structure, the need for two pumps and the high fluid dynamic energy loss in the cross flow chamber: the use of this device on an industrial scale to perform the hydroformylation is almost non- Economical.

A generic device as discussed at the outset is known from WO 2013/034690 A1. Here, the membrane separation unit is disposed in an external liquid circuit of the jet loop reactor. In addition to the percentage of liquid, one of the disadvantages of this device is that the fluid conducted through the outer liquid loop also transports a percentage of gas - dissolved in the liquid phase or in the gas phase. Therefore, the volume that must be conducted through the membrane separation unit is quite large. The high feed volume flow rate for the membrane separation unit requires a high membrane surface area and, therefore, a relatively high capital cost for setting up the system. Moreover, some separator materials are not available at all in a large number, so that a membrane separation unit having a large membrane surface area made of the membrane material can also be economically produced.

In contrast to the prior art, it is an object of the present invention to reduce the cost of the device.

This is surprisingly achieved by providing an additional device, ie a gas separator, which is arranged in the external liquid circuit of the jet loop reactor and is installed for separating the gas from the external liquid Loop and will Gas is fed back into the jet loop reactor.

The invention therefore relates to a device for the continuous homogeneous catalytic reaction of a liquid with a gas and optionally another fluid, wherein the device comprises at least one jet loop reactor having an external liquid loop driven by at least one pump, wherein The apparatus has at least one membrane separation unit, preferably retaining the homogeneous catalyst, the membrane separation unit being disposed in an external liquid loop of the jet loop reactor, and wherein

A gas separator is disposed in an outer liquid loop of the jet loop reactor, the gas separator being configured to separate gas from the outer liquid loop and feed the gas back into the jet loop reactor.

The present invention is based on the knowledge that the percentage of gas can be removed by the gas separator by the gas separator before it is passed through the membrane. The gas separator can separate not only the gas dissolved in the liquid phase but also the gas forming the separated gas phase (bubble) by the fluid conducted in the liquid loop. The outgassing in the gas separator is reduced to the feed volume flow rate of the membrane separation unit, whereby the membrane surface area and thus the cost of the membrane separation unit can also be reduced. Since gas separators are relatively inexpensive and simple to use standard equipment, the combination of membrane separation unit with upstream gas separator and reduced membrane surface area is less expensive than conventional units that do not have a gas separator but require a higher membrane surface area. According to the present invention, for the same separation efficiency of the membrane separation unit, the separator separation unit has a smaller membrane surface area than in the prior art.

Another advantage of the gas separator is that many commercially available membrane modules are not suitable for reaction mixing with dissolved and/or undissolved gas percentages. Because these are not designed for adequate gas removal on the side of the permeate, and depending on the amount of volumetric gas flow to be removed on the side of the permeate, establish a back pressure on the side of the permeate, It reduces the liquid permeate output or can even cause damage to the membrane.

In order to avoid deactivation of the catalyst and damage to the membrane due to outgassing, and also to achieve improved membrane retention, it is conventional in conventional systems to degas the permeate of the membrane separation unit. Due to the gas separator according to the invention, such measures are no longer absolutely necessary, since the harmful gas percentage has been removed before the membrane separation unit. In contrast to this prior art, the outgassing continues on the feed side and not on the permeate side in accordance with the present invention. However, despite previous degassing, post-degassing of the sides of the permeate may be desirable if the homogeneous catalyst must be stabilized during separation of the membrane with dissolved gases.

A particular development of the invention is provided in the external liquid circuit, upstream of the membrane separation unit, the heat exchanger is configured to cool the feed of the membrane separation unit, and the gas separator is disposed in the heat exchanger Downstream and upstream of the membrane separation unit. This heat exchanger has a function of removing the heat of reaction of the exothermic reaction. It is expedient to arrange the gas separator downstream of the heat exchanger because the liquid loop then has a lower temperature and therefore it can be preferably degassed. Moreover, the higher temperatures in many separator materials thereby result in a reduction in the retention of the membrane and thereby a reduction in the separation. The pump for moving the outer liquid circuit is preferably disposed upstream of the diaphragm separation unit. In particular, it is also arranged upstream of the gas separator and - if a heat exchanger is provided in the liquid circuit - in the Upstream of the heat exchanger.

A preferred development of the invention provides that the membrane separation unit is fabricated as a multi-stage membrane assembly. The permeate quality can be improved thereby and/or the membrane surface area is reduced.

As a diaphragm ensemble, in this case, consider the Christmas tree interconnection or feed and release systems, especially such as enrichment or stripping.

In this simple case, the membrane separation unit is made as a feed and discharge system with a single recirculation loop (referred to as a looper). In the recirculation loop, a portion of the retentate is fed back into the feed.

The permeate quality can be improved first, wherein the membrane separation unit is made up of a plurality of series circuits.

In addition, the permeate quality can be improved, wherein a multi-stage feed and discharge system is used as the membrane separation unit. In this case, it is a multi-stage diaphragm assembly with a plurality of recirculation loops or loops. The tandem feed and discharge diaphragm system can be made into either a "peeling set" or an "enrichment set". Each stage of this set can be made from one or more loops.

In contrast to the "Christmas Tree Interconnect" familiar to the diaphragm technology and thus known (Milan/Lautaubach), the diaphragm assembly that is made into the feed and discharge system allows for variations in quality and/or quantity. Operate under feed conditions and/or in cases where diaphragm performance changes over time. At high concentration factors, for the same installed diaphragm surface area, stripping integration results in better overall permeate quality than enrichment. Furthermore, enrichment clustering has the disadvantage that the required surface area is more than twice as large as compared to a single-stage membrane separation unit. In the case of stripping the ensemble, in contrast, virtually any desired diaphragm surface The product energy is used between the single-stage membrane separation unit and the enrichment assembly. This is important, especially when the enrichment set is uneconomical due to the high membrane surface area required, and the single stage membrane separation unit is not available due to insufficient separation.

Under these prerequisites, the use of a secondary membrane manifold with local permeate recirculation is used as a membrane separation unit to come to mind. In this case, the permeate system is recirculated by the recirculation loop or a loop having the least desirable permeate quality, which is substantially at the end of the concentration section having the highest retentate concentration loop . This interconnection is referred to as "secondary stripping integration" in the diaphragm technology. A recirculation loop having permeate recirculated at the end of the collection is also referred to as a concentration loop. The interconnection of the concentrate loop with permeate recirculation allows for a purer total permeate.

Very particularly preferably, the membrane surface area used in the concentrate circuit is made to be smaller than the membrane surface used in the conventional circuit. In this way, the separation result is not attenuated and the diaphragm surface area demand is reduced.

Alternatively, the membrane separation unit is made as a secondary enrichment cluster. The secondary enrichment set is associated with a multi-stage membrane assembly with local retentate recycle. In this case, the total retentate from this second stage is recycled. Not only is the first stage of the secondary enrichment set, but the second stage can be made of one or more diaphragm circuits. In contrast to the stripping assembly, first of all, the concentration factor required here is sufficiently low that the enrichment cluster is advantageous due to the separation. Secondly, the total permeate is produced, and thus the required membrane surface area is sufficiently small to make the enrichment integration economical.

A particularly preferred embodiment of the invention is provided in which no transport element is provided between the gas separator and the jet loop reactor, such that the jet loop reactor is separated from the external liquid loop The manner in which the separator gas is independently absorbed. This is because the strong internal liquid flow through the jet loop reactor acts as a water jet pump, and thus the percentage of gas separated in the gas separator of the external liquid loop without additional units can be recycled to The way of the reactor. In this regard, no transport element means that no direct transport element, such as a pump, is provided between the gas separator and the jet loop reactor. The transport output is ultimately provided by the pump that produces the external liquid loop and the flow in the reactor, and thus indirectly causes the pump effect.

In another preferred embodiment of the present invention, a tubular reaction space extends in the jet loop reactor, a jet nozzle for injecting the liquid into the reaction space opens into the space, and is used for inhalation of the inhaled gas. The tube is also opened in conjunction, and a baffle shielded output for the external liquid circuit is provided in the space.

The jet nozzles in the upright extension reactor can be directed upwards or downwards. The opening of the jet nozzle and the suction tube causes an intensive mixing of the liquid and gas reaction components (pump effect). The gas may be drawn from the outside by suction through the suction pipe or by suction in a region within the reaction space, and the gas bubble extends in the reaction space. The output can be configured at the top or bottom of the reactor. Shielding the output by the baffle reduces bubble introduction from the internal liquid circuit to the external liquid circuit. For the improvement of the flow dynamics, at least one guiding tube extending concentrically through the reaction space can be raised for. As a result, the mixing of the liquid phase and the gas phase is enhanced. A plurality of guide tubes can also be configured for front-to-back alignment. The reaction mixture then flows through the guide tube in the main flow direction, is deflected at the end of the guide tube, and flows back outside the guide tube. The guide tube represents a structural separation of the flow direction of the inner loop.

The apparatus according to the invention is suitable for use in a homogeneous manner for a homogeneous catalytic reaction of a liquid with a gas and optionally another fluid, wherein at least one target product which reacts with the permeate of the membrane separation unit is discharged from the liquid circuit.

The invention therefore also relates to a process for the homogeneous catalytic reaction of a liquid with a gas, and optionally another fluid, wherein the reaction is carried out in a device according to the invention, and wherein at least one target product of the reaction The permeate of the membrane separation unit is discharged from the liquid loop.

Due to the gas separator, it is possible to handle a liquid loop having a gas percentage. This is possible up to a percentage of gas of about 30% by volume of the feed to the membrane separation unit. A preferred development of the method according to the invention is therefore upstream of the membrane separation unit, the external liquid circuit comprising a mixture of liquid and gas phases distributed therein, wherein the volume fraction of the gas phase is zero And between 30%.

However, the gas separator also allows for a relatively high amount of gas to be processed. A preferred development of the method according to the invention is therefore upstream of the gas separator, the external liquid circuit comprising a mixture of liquid and gas phases distributed therein, wherein the volume fraction of the gas phase is 30 And between 100%. Downstream, so that after the gas separator is fed into the membrane separation unit, less than 30% by volume of gas is present In this manner, the gas separator then has the effect of separating the higher gas percentage, which does not damage the membrane.

These reactions can be two-phase (liquid/gas) or three-phase (liquid/liquid/gas or liquid/gas/gas). A small amount of solids may also be present in the liquid loop.

Examples of reactions that can be carried out are oxidation, epoxidation, hydroformylation, hydroamination, hydrogen aminomethylation, hydrocyanation, hydrocarboxyalkylation, amination, ammoxidation, Deuteration, hydrogenation decylation, ethoxylation, propoxylation, carbonylation, short chain polymerization, displacement, Suzuki coupling or hydrogenation.

Particularly preferably, the apparatus is suitable for use in hydroformylation, that is, a compound having an olefinic double bond is reacted with a synthesis gas to form acetaldehyde and/or ethanol.

The use of the apparatus for carrying out the method is likewise the subject of the invention.

The device according to the invention can be used in particular for the reaction of a liquid with a gas, wherein not only the gas but also the liquid has at least one reactant.

The reaction products are discharged in the liquid phase along with the permeate.

In the apparatus according to the invention, the reaction can be carried out in a pressure range of from 0.2 to 40 MPa (absolute) and a temperature range of from 0 to 350 °C. In this case, the reaction preferably occurs with the accompanying catalyst homogeneously dissolved in the liquid phase.

Preferably, in the device according to the invention, the reaction is carried out, The catalyst is fed by the liquid feed, and is homogeneously dissolved in the liquid by, for example, hydroformylation of cobalt carbonyl or carbonyl hydrazine with or without the addition of a phosphorus-containing ligand by a compound having an olefinic double bond. In the product/reactant phase, such as the production of acetaldehyde and/or ethanol.

The choice of a suitable membrane material will be made relative to the catalyst composite to be separated: since the membrane is a function of the permeability of the various components of the feed to be separated, which is not absolutely impervious to the catalyst, The reaction participant is compared, the rate of passage is inversely slower, and the membrane must be selected in such a way that it preferentially retains the catalyst complex to be separated.

In the process according to the invention, the separator can be used, due to its chemical or physical properties, it is suitable to retain the organophosphorus metal composite catalyst and/or the organophosphorus-free ligand preferably in a range of at least 50%. .

The corresponding diaphragm belongs to the grade of the nanofiltration membrane. The expression of nanofiltration is applied to a membrane separation process having a separation limit or a molecular weight retention (MWCO) in the range of from 150 g/mol to more than 1 nm. The size of the separation limit (or molecular weight of the carrier - MWCO) indicates the molecular or particle size of the component with 90% of the membrane retention.

The usual method of determining the separation limit is given to Y.H. See Toh, X.X. Loh, K. Li, A. Bismarck, A. G. Livingston, Standard Methods for Finding Illustrative Properties for Organic Solvent Nanofiltration Membranes, J. Membr. Sci., 291 (2007) 120-125.

The membrane holding R _i is calculated from the feed side concentration of the component i discussed in the membrane x _iF and the permeate side concentration of the component i discussed in the membrane x _iP as follows: R _i =1-x _iP / x _iR

Preferably, the membrane for this application according to the invention will have a MWCO of less than 1000 g/mol.

Another prerequisite for the availability of the membrane is that the membrane must be stable to all compounds present in the reaction mixture, especially for such solvents. The membrane is also considered to be stable, for example by swelling of the membrane polymer - undergoing a change over time in MWCO and/or permeability, but the separation is satisfied throughout the period of operation. Again, the membrane material will withstand the reaction temperature. The membrane material that is stable at the reaction temperature and applied at the reaction temperature allows the temperature control of the composite to be dispensed with.

Preference is given to using a separator having a separating active layer of a material selected from the group consisting of cellulose acetate, cellulose triacetate, cellulose nitrate, regenerated cellulose, polyimine, polyamine, polyetheretherketone, sulfuric acid Polyetheretherketone, aromatic polyamine, polyamidoximine, polybenzimidazole, polybenzimidazolone, polyacrylonitrile, polyarylene sulfide, polyester, polycarbonate, polytetrafluoroethylene Ethylene, polyvinylidene fluoride, polypropylene, polydimethyloxane, hydrazine, polyphosphazene, polyphenylene sulfide, polybenzimidazole, nylon® 6,6, polyfluorene, polyaniline, polyurethane, acrylonitrile /ethylene glycol methacrylate (PANGMA), polytrimethylene propyne, polymethylpentene, polyvinylidene fluoride, alpha alumina, titania, gamma alumina, polyphenylene ether, cerium oxide, zirconium oxide, Ceramic separators hydrophobized with decane, as described in DE 10308111, having a microporous (PIM) polymer, such as PIM-1 and others, such as It is described in I. Kabasso, Encyclopedia of Polymer Science and Technology, John Wiley and Children, New York, EP 0 781 166, 1987, and in "Separator". The foregoing substances may be especially present in the separation active layer, optionally in the form of cross-linking through the addition of an adjuvant, or as a mixed matrix membrane with a filler, such as a carbon nanotube, a metal organic framework or a hollow Spheres, and particulates of inorganic or inorganic fibers, such as ceramic fibers or glass fibers, are provided.

A particular preference is given to the use of a membrane having a polymer layer as a separation active layer consisting of polydimethyloxane, polyimine, polyamidimide, acrylonitrile/ethylene glycol. Made of methacrylate (PANGMA), polydecylamine or polyetheretherketone, which is composed of a polymer having microporous (PIM) such as PIM-1, or wherein the separation active layer is It consists of a hydrophobic ceramic diaphragm. Very particularly preferably, a membrane made of hydrazine or polyamidimide is used. Such membranes are commercially available.

And the aforementioned materials, the separators may include further materials. More particularly, the membranes may comprise a support or carrier material to which the separation active layer has been applied. In such synthetic membranes, the support material is still present as well as the actual membrane. The choice of support material is described by EP 0 718 166, which is expressly incorporated by reference.

The choice of commercially available nanofiltration membranes comes from the MPF and Selro series from Coriolis Diaphragm Systems, the different types of Solsep BV, the Starmem ^TM series from Grace/UOP, the DuraMem ^TM and PuraMem ^TM series from Evonik Industries, from Bio-Pure Technologies' Nano-Pro series, HITK-T1 from IKTS, and also from oMT-1, oNF-2 and NC-1 from GMT Membrantechnik GmbH. When the injection loop reactor and the membrane separation unit are disposed in a shared external liquid loop, this has the effect of having the same yield through the reactor and the membrane. However, the yield performance of the reactor and membrane can vary for reasons of a particular equipment. Then, nevertheless, in order to achieve a liquid loop or an ideal diaphragm overflow, it is possible to equip the apparatus having this low flow-through performance with a bypass conduit that allows partial bypassing of the hydraulic barrier. Accordingly, the apparatus has at least one bypass conduit disposed in the outer liquid circuit parallel to the jet loop reactor or the diaphragm separation unit.

In another preferred embodiment of the apparatus, it has more than one jet loop reactor, but instead has a plurality of parallel connectable loop loop reactors and has a shared external liquid loop wherein the membrane is separated The unit is configured within the shared external liquid loop. By opening and closing individual reactors, the size is designed to be a relatively small number of jet loop reactors that allow for flexibility in the conversion performance of the device at that desired location. This allows the device to be economically utilized under changing requirements.

The membrane separation unit can also be made to operate in parallel: by opening and closing the individually parallel connected membrane modules, the entire membrane surface area of the membrane separation unit can be resiliently designed to suit the system's capabilities. A preferred development of the present invention is thus characterized by a membrane separation unit such that the entire active membrane surface area of the membrane separation unit can be adjusted by opening and closing the membranes, the membrane separation unit comprising level Most of the diaphragms connected by the ground.

1‧‧‧Spray loop reactor

2‧‧‧Reaction space

3‧‧‧Liquid surface

4‧‧‧jet nozzle

5‧‧‧ gas feed

6‧‧‧ Guide tube

7‧‧‧Baffle

8‧‧‧ Output

9‧‧‧External liquid loop

10‧‧‧

11‧‧‧ heat exchanger

12‧‧‧ gas separator

13‧‧‧ gas conduit

14‧‧‧Separator separation unit

15‧‧‧Feed in

16‧‧‧through

17‧‧‧Retentate

18‧‧‧Reagents

19‧‧‧ first level

20‧‧‧ second level

21‧‧‧The pump in the diaphragm separation unit

22‧‧‧(first) pressure rise pump

23‧‧‧ third level

24‧‧‧Second pressure rise pump

25‧‧‧ rear deaerator

26‧‧‧Exhaust

27‧‧‧Isolation by distillation

28‧‧‧First target product

29‧‧‧ second target product

30‧‧‧ level pump

31‧‧‧ circuit

The invention will now be described in detail by way of exemplary embodiments. The drawings show: Figure 1: a device according to the invention with a simple membrane separation unit; Figure 2: a detailed view of the membrane separation unit as a secondary stripping assembly; Figure 3: as a secondary enrichment set Detailed view of the second membrane unit in conjunction; Figure 4: Apparatus according to the invention having a membrane separation unit in the assembly and a permeate treated by distillation.

Figure 1 shows a first embodiment of a device having a jet loop reactor 1 in accordance with the present invention. The jet loop reactor 1 comprises a tubular reaction space 2 in the form of a pressure tube which is filled with a liquid reaction mixture up to the defined liquid surface 3. Gas bubbling of the gas reaction component is formed above the surface of the liquid. Because the solution is equilibrated, the gaseous reaction partners are partially dissolved in the liquid reaction mixture; the local gas reaction is present in the liquid such as the gas phase (shown as bubbles in the illustration). The homogeneous catalyst is likewise dissolved in the reaction liquid.

The jet nozzle 4 is projected downward into the liquid reaction mixture, via which The spray nozzle, the liquid reaction participant, is injected with high kinetic energy. The gas reaction participant enters the reaction space 2 through a gas feed 5 . The suction duct is structurally assigned to the jet nozzle 4, which sucks the gas from the gas filling portion of the reaction space 2 by suction and mixes it with the liquid stream. For this purpose, the openings of the suction pipe and the jet nozzle are brought into close proximity and jointly into the reaction space. Due to the high flow velocity of the liquid reaction participant exhibited by the jet nozzle 4, the gas reaction participants from the gas feed 5 are entrained (comparable to the water jet pump).

The guiding tube 6 extends concentrically and axially through the reaction space 2 to the pressure tube. The guiding tube 6 has a function of providing an internal liquid circuit in the reaction space 2: the injection reaction liquid flows downward from the injection nozzle 4 through the guiding tube 6, and is disposed at the other end of the reaction space 2. The baffle 7 of the portion is biased, and in this way, the flow is caused to flow upward again outside the guide tube 6. In this way, an internal liquid loop is formed in the reaction space 2, in which the reaction partners are densely mixed and reacted.

An output 8 is provided below the baffle 7, through which the reaction mixture is continuously removed from the reaction space 2 and fed into the external liquid circuit 9. The baffle 7 shields the output 8 by the internal liquid circuit and thereby allows the bubble to hardly reach the external liquid circuit 9. The external liquid loop thus consists essentially of liquid reactants, dissolved catalyst, and dissolved gaseous reactants.

For practical measures of the present invention, whether or not the jet nozzle 4 is guided downward and whether the shutter 7 is disposed below the jet nozzle 4 is independent. Its system It is also possible to inject upward from the bottom of the reactor. In both cases, the output can be configured at the top or bottom of the reactor. The baffle must accordingly be configured in such a way that it shields the output.

The outer liquid circuit 9 is moved by the pump 10. The pump 10 series peripheral impeller pump is also capable of transporting liquid/gas mixtures. Tiny bubbles are therefore harmless.

Downstream, after the pump 10, the heat exchanger 11 is arranged, by means of which the thermal energy is introduced into or discharged from the external liquid circuit 9 depending on the type of reaction. Furthermore, the jet loop reactor 1 itself can be provided with a heat exchanger (not shown) surrounding the reaction space. When, for example, an exothermic reaction is carried out, such as hydroformylation, the heat of the reaction is removed by the heat exchanger 11. The heat exchanger 11 then cools the outer liquid circuit 9.

Downstream, after the heat exchanger 11, the gas separator 12 is configured. The gas separator 12 separates the gas percentage from the external liquid circuit 9 and feeds these to the jet loop reactor 1. For this purpose, the gas separator 12 is connected to the gas feed 5 of the jet loop reactor 1 via a gas conduit 13. In the gas conduit 13, no transport element is configured because the jet loop reactor independently draws gas separated from the gas separator 12 by suction.

Downstream, after the gas separator 12, the membrane separation unit 14 is configured. Regarding any diaphragm, the membrane separation unit 14 has three connections, namely a feed 15, a permeate 16 and a retentate 17. The reaction mixture flowing in via the feed 15 is separated into the permeate 16 and retained in the membrane Matter 17. Since the membrane has less permeability to the dissolved catalyst composite than to the retained component of the feed 15, the catalyst remains on this side of the membrane and is enhanced in the retentate 17. The membrane separation unit 14 has a preferred permeability of the valuable product relative to the catalyst and thereby provides a means for enhancing the valuable product relative to the catalyst in the permeate 16. The permeate 16 is further conducted for processing (not shown in Figure 1); the catalyst-rich retentate 17 is returned, mixed with fresh liquid reagent 18, and passed into the reactor 1 via the jet nozzle 4.

The gas separator 12 disposed upstream of the membrane separation unit 14 according to the present invention achieves a reduction in the volumetric flow rate to the feedthrough 15 of the membrane separation unit 14, since the bubble and dissolved gas system are separated from the external liquid loop 9. And directly recirculated into the jet loop reactor 1 via the gas conduit 13. Due to the reduced feed volumetric flow rate, the membrane separation surface of the membrane separation unit 14 can be smaller than conventional systems without the gas separator 12 for the same separation performance. In particular, it has become significantly more economical to perform catalytic hydroformylation homogeneously because the separation of the ruthenium phosphite complex catalyst used in this case requires an expensive separator.

In Figure 1, the membrane separation unit 14 is shown in its simplest design with only one diaphragm. In fact, the membrane separation unit 14 is preferably made as a multi-stage membrane assembly, as shown in Figures 2 and 3.

Figure 2 shows the schematic structure of a membrane separation unit 14 designed to have a secondary stripping assembly of secondary stages 19, 20. The degassing feed 15 is applied to the first stage 19. The permeate of the first stage 19 corresponds to the separator separation sheet The result of element 14 is transmitted through substance 16. The retentate of the first stage 19 is applied to the second stage 20 without further pressure rise. The retentate of the second stage 20 corresponds to the resulting retentate 17 of the membrane separation unit 14. The permeate of the second stage 20 is mixed with the feed 15 of the membrane separation unit 14 and fed back to the first stage 19 via the internal pump 21. The permeate of the second stage 20 thus corresponds to the internal permeate recirculation of the membrane separation unit 14 which is made to strip the collection.

Figure 3 shows the schematic structure of a membrane separation unit 14 designed to have a secondary enrichment set of secondary stages 19, 20. The degassing feed 15 is applied to the first stage 19. The retentate of the first stage 19 corresponds to the resulting retentate 17 of the membrane separation unit 14 and leaves the retentate. The permeate of the first stage 19 is again pressurized by the second pressure rise pump 24 to rebalance the transmembrane pressure of the first stage 19. Thereafter, the second stage 20 of separation of the diaphragm continues. The permeate produced in this case corresponds to the result permeate 16 of the entire membrane separation unit 14. The retentate of the second stage 20 is mixed with the feed 15 and recirculated to the first stage 19 via a first pressure rise pump 22 . The retentate of the second stage 20 is thus refluxed by the internal retentate of the enriched set.

Figure 4 shows a device according to the invention, wherein the membrane separation unit 14 has three membrane stages 19, 20, 23 connected front to back in the direction of the permeate. The two pressure rise pumps 22, 24 equalize the transmembrane pressure that has been reduced at this level 19, 20. The individual retentates of stages 19, 20, 23 are combined into the resulting retentate 17 and recycled to the jet loop reactor 1. Each level 19, 20, 23 also includes a separate stage pump 30 and an internal circuit 31, as in This is shown in the detailed magnification of the first stage 19.

The permeate of the third stage 23 forms the permeate 16 of the membrane separation unit 14. The residual gas component is degassed in the after-gas eliminator 25, and the residual gas component is not separated by the gas separator 12, for example, for the catalyst composite via the tertiary stages 19, 20, 23 during the catalyst separation. Stabilization of things. Because of the pressure drop occurring therebetween, the gas separated in the rear deaerator 25 cannot be recycled to the jet loop reactor 1 without compression, and is therefore discarded as exhaust gas 26 for simplicity.

At the same time, the gas separated in the gas separator 12 still does not encounter the membrane and can therefore be recycled back to the jet loop reactor 1 via the gas conduit 13 without the transport element. Here, it is fed separately from the gaseous reactant 18, that is to say without feeding through the shared gas.

In Figure 4, the isolation purification 27 is further shown by distillation of the post-degassed permeate 16, during which the actual target products 28, 29 are obtained. The target products are n-butyraldehyde 28 and isobutyraldehyde 29 which are produced by the hydroformylation of propylene with carbon monoxide and hydrogen (synthesis gas) and all reagents 18. The gas separated in the gas separator 12 is substantially the unreacted gas.

1‧‧‧Spray loop reactor

2‧‧‧Reaction space

3‧‧‧Liquid surface

4‧‧‧jet nozzle

5‧‧‧ gas feed

6‧‧‧ Guide tube

7‧‧‧Baffle

8‧‧‧ Output

9‧‧‧External liquid loop

10‧‧‧

11‧‧‧ heat exchanger

12‧‧‧ gas separator

13‧‧‧ gas conduit

14‧‧‧Separator separation unit

15‧‧‧Feed in

16‧‧‧through

17‧‧‧Retentate

18‧‧‧Reagents

Claims (12)

An apparatus for continuous homogeneous catalytic reaction of a liquid with a gas and optionally another fluid, wherein the apparatus comprises at least one jet loop reactor having an external liquid loop driven by at least one pump, and wherein the apparatus Having at least one membrane separation unit, preferably retaining the homogeneous catalyst, the membrane separation unit being disposed in an outer liquid loop of the jet loop reactor, characterized in that a gas separator is disposed in the jet loop reactor In the outer liquid loop, the gas separator is installed to separate the gas from the outer liquid loop and feed the gas back into the jet loop reactor. The apparatus of claim 1, wherein in the external liquid loop, upstream of the membrane separation unit, the heat exchanger is configured to cool the feed of the membrane separation unit, and wherein the gas separator is It is disposed downstream of the heat exchanger and upstream of the membrane separation unit. The apparatus of claim 1 or 2, wherein the pump is disposed upstream of the diaphragm separation unit, in particular wherein the pump is disposed upstream of the gas separator, and particularly preferably Upstream of the heat exchanger. The apparatus of claim 1 or 2, wherein the membrane separation unit is formed as a multi-stage membrane assembly. The apparatus of claim 1 or 2, wherein the transport element is provided in such a manner that the jet loop reactor independently absorbs the gas separated by the external liquid loop by the gas separator Between the gas separator and the jet loop reactor. The apparatus of claim 1 or 2, wherein the tubular reaction space extends in the jet loop reactor, a jet nozzle for injecting the liquid into the reaction space opens into the space, and is used for inhalation of the inhaled gas. The tube is also opened in conjunction, and a baffle shielded output for the external liquid circuit is provided in the space. A method for the homogeneous catalytic reaction of a liquid with a gas and optionally another fluid, characterized in that the reaction is carried out in a device according to any one of claims 1 to 6, and wherein the reaction is at least A target product is discharged from the liquid loop along with the permeate of the membrane separation unit. The method of claim 7, wherein the external liquid loop comprises a mixture of a liquid phase and a gas phase dispersedly distributed therein, wherein the volume fraction of the gas phase is zero And between 30%. The method of claim 10, wherein, upstream of the gas separator, the external liquid circuit comprises a mixture of a liquid phase and a gas phase dispersedly distributed therein, wherein the volume fraction of the gas phase is 30 And between 100%. For example, in the method of claim 7, 8 or 9, wherein oxidation, epoxidation, hydroformylation, hydroamination, hydrogen aminomethylation, hydrocyanation, hydrocarboxyalkylation, amine Chemistry, ammoxidation, deuteration, hydrogenation, ethoxylation, ethoxylation Action, propoxylation, carbonylation, short chain polymerization, displacement, Suzuki coupling or hydrogenation are carried out in the apparatus. The method of claim 10, wherein the compound having an olefinic double bond is reacted with a synthesis gas by hydroformylation to form acetaldehyde and/or ethanol. Use of a device according to any one of claims 1 to 6 for carrying out a homogeneous catalytic reaction, in particular for hydroformylation.